Hydrosilane σ‐Adduct Intermediates in an Adaptive Zinc‐Catalyzed Cross‐dehydrocoupling of Si−H and O−H Bonds

Three‐coordinate (Ph)BOX [Formula: see text] ZnR ((Ph)BOX [Formula: see text] =phenyl‐(4,4‐dimethyl‐oxazolinato; R=Me: 2 a, Et: 2 b) catalyzes the dehydrocoupling of primary or secondary silanes and alcohols to give silyl ethers and hydrogen, with high turnover numbers (TON; up to 10(7)) under solvent‐free conditions. Primary and secondary silanes react with small, medium, and large alcohols to give various degrees of substitution, from mono‐ to tri‐alkoxylation, whereas tri‐substituted silanes do not react with MeOH under these conditions. The effect of coordinative unsaturation on the behavior of the Zn catalyst is revealed through a dramatic variation of both rate law and experimental rate constants, which depend on the concentrations of both the alcohol and hydrosilane reactants. That is, the catalyst adapts its mechanism to access the most facile and efficient conversion. In particular, either alcohol or hydrosilane binds to the open coordination site on the (Ph)BOX [Formula: see text] ZnOR catalyst to form a (Ph)BOX [Formula: see text] ZnOR(HOR) complex under one set of conditions or an unprecedented σ‐adduct (Ph)BOX [Formula: see text] ZnOR(H−SiR′(3)) under other conditions. Saturation kinetics provide evidence for the latter species, in support of the hypothesis that σ‐bond metathesis reactions involving four‐centered electrocyclic 2σ–2σ transition states are preceded by σ‐adducts.